Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes

Abstract

Vinyl carbonate endcapped polysiloxanes containing a fluorinated side chain are useful as biomaterials, especially hydrogel biomaterials, including contact lens materials.

1. A hydrogel that is the hydrated polymerization product of a monomer mixture comprising a hydrophilic monomer, and a monomer of the formula: 
                 
 wherein:  
 each R is independently an alkylene group having 1 to 10 carbon atoms which may have ether linkages between carbon atoms;  
 each R′ is independently a monovalent hydrocarbon radical or a halogen substituted monovalent hydrocarbon radical having 1 to 18 carbon atoms which may have ether linkages between carbon atoms;  
 each R 3  is hydrogen or methyl  
 w and x are each ≧0;  
 y is ≧1;  
 w+x+y=2 to 1000; and  
 R ″  is a fluorinated side chain of the formula —D—(CF 2 ) 2 —H, wherein z is 1 to 20, and D is an alkylene group having 1 to 10 carbon atoms which may have ether, carbonate, carbamate, ester or amide linkages between carbon atoms,  
 wherein said hydrogel has an oxygen permeability of at least about 120 Barrers, a water content of at least about 20 weight percent, and a modulus no greater than about 97 g/mm 2 .  
 
     
     
       2. The hydrogel of  claim 1 , wherein said monomer mixture further comprises a monofunctional polysiloxanylalkyl monomer. 
     
     
       3. The hydrogel of  claim 2 , wherein the monofunctional polysiloxanylalkyl monomer is represented by the formula: 
                 
 wherein:  
 X denotes —OCOO—, or —OCONR 4 — where each R 4  is H or lower alkyl;  
 R 3  denotes hydrogen or methyl;  
 h is 1 to 10; and  
 each R 2  independently denotes a lower alkyl or halogenated alkyl radical, a phenyl radical or a radical of the formula —Si(R 5 ) 3  wherein each R 5  is independently a lower alkyl radical or a phenyl radical.  
 
     
     
       4. The hydrogel of  claim 3 , wherein the monofunctional polysiloxanylalkyl monomer is selected from the group consisting of 3-[tris(trimethylsiloxy)silyl] propyl vinyl carbamate and 3-[tris(trimethylsiloxy)silyl] propyl vinyl carbonate. 
     
     
       5. The hydrogel of  claim 1 , wherein said hydrophilic monomer is selected from the group consisting of N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl-formamide, N-vinyl-2-pyrrolidone, and mixtures thereof. 
     
     
       6. The hydrogel of  claim 5 , wherein the hydrophilic monomer includes N-vinyl-2-pyrrolidone. 
     
     
       7. The hydrogel of  claim 1 , wherein R ″  is —CH 2 —CH 2 —CH 2 —O—CH 2 —(CF 2 ) 4 —H. 
     
     
       8. A contact lens made from the polymerization product of a monomer mixture which comprises a vinyl carbonate endcapped polysiloxane containing a fluorinated side chain, wherein said contact lens is composed of a hydrogel having an oxygen permeability of at least about 120 Barrers, a water content of at least about 20 weight percent, and a modulus no greater than about 97 g/mm 2 . 
     
     
       9. The contact lens of  claim 8 , wherein the vinyl carbonate endcapped polysiloxane is of the formula: 
                 
 wherein:  
 each R is independently an alkylene group having 1 to 10 carbon atoms which may have ether linkages between carbon atoms;  
 each R′ is independently a monovalent hydrocarbon radical or a halogen substituted monovalent hydrocarbon radical having 1 to 18 carbon atoms which may have ether linkages between carbon atoms;  
 each R 3  is hydrogen or methyl  
 w and x are each ≧0;  
 y is ≧1;  
 w+x+y=2 to 1000; and  
 R ″  is a fluorinated side chain of the formula —D—(CF 2 ) z —H, wherein z is 1 to 20, and D is an alkylene group having 1 to 10 carbon atoms which may have ether, carbonate, carbamate, ester or amide linkages between carbon atoms.  
 
     
     
       10. The contact lens of  claim 9 , wherein the monomer mixture further comprises a hydrophilic monomer. 
     
     
       11. The contact lens of  claim 10 , wherein said hydrophilic monomer is selected from the group consisting of N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl-formamide, N-vinyl-2-pyrrolidone, and mixtures thereof. 
     
     
       12. The contact lens of  claim 11 , wherein the hydrophilic monomer includes N-vinyl-2-pyrrolidone. 
     
     
       13. The contact lens of  claim 10 , wherein said monomer mixture further comprises a monofunctional polysiloxanylalkyl monomer. 
     
     
       14. The contact lens of  claim 13 , wherein the monofunctional polysiloxanylalkyl monomer is represented by the formula: 
                 
 wherein:  
 X denotes —OCOO—, or —OCONR 4 — where each R 4  is H or lower alkyl;  
 R 3  denotes hydrogen or methyl;  
 h is 1 to 10; and  
 each R 2  independently denotes a lower alkyl or halogenated alkyl radical, a phenyl radical or a radical of the formula —Si(R 5 ) 3  wherein each R 5  is independently a lower alkyl radical or a phenyl radical.  
 
     
     
       15. The contact lens of  claim 14 , wherein the monofunctional polysiloxanylalkyl monomer is selected from the group consisting of 3-[tris(trimethylsiloxy)silyl] propyl vinyl carbamate and 3-[tris(trimethylsiloxy)silyl] propyl vinyl carbonate. 
     
     
       16. The contact lens of  claim 9 , wherein R ″  is —CH 2 —CH 2 —CH 2 —O—CH 2 —(CF 2 ) 4 —H.